US5998096A - Process for producing polymerization or crosslinking rate-distributed article and process for producing lens, lens array or waveguide using the process - Google Patents

Process for producing polymerization or crosslinking rate-distributed article and process for producing lens, lens array or waveguide using the process Download PDF

Info

Publication number
US5998096A
US5998096A US08/886,422 US88642297A US5998096A US 5998096 A US5998096 A US 5998096A US 88642297 A US88642297 A US 88642297A US 5998096 A US5998096 A US 5998096A
Authority
US
United States
Prior art keywords
lens
distribution
photo
refractive index
lens array
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US08/886,422
Inventor
Seiji Umemoto
Yasuo Fujimura
Kazutaka Hara
Suguru Yamamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP18302192A external-priority patent/JPH063506A/en
Priority claimed from JP25058992A external-priority patent/JP3181998B2/en
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to US08/886,422 priority Critical patent/US5998096A/en
Application granted granted Critical
Publication of US5998096A publication Critical patent/US5998096A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00Producing optical elements, e.g. lenses or prisms
    • B29D11/00009Production of simple or compound lenses
    • B29D11/00278Lenticular sheets
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B3/0006Arrays
    • G02B3/0012Arrays characterised by the manufacturing method
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B3/0006Arrays
    • G02B3/0037Arrays characterized by the distribution or form of lenses
    • G02B3/005Arrays characterized by the distribution or form of lenses arranged along a single direction only, e.g. lenticular sheets
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B3/0006Arrays
    • G02B3/0037Arrays characterized by the distribution or form of lenses
    • G02B3/0056Arrays characterized by the distribution or form of lenses arranged along two different directions in a plane, e.g. honeycomb arrangement of lenses
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B3/0087Simple or compound lenses with index gradient
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B6/13Integrated optical circuits characterised by the manufacturing method
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0838Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using laser
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12035Materials
    • G02B2006/12069Organic material
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B3/0006Arrays

Definitions

  • This invention relates to a process for producing a polymer having an uneven distribution of a polymerization rate or a crosslinked article having an uneven distribution of a crosslinking rate.
  • the process is applicable to formation of microlenses having an uneven distribution of refractive index.
  • polymerization rate-distributed polymer a polymer having an uneven distribution of a polymerization rate, i.e., a polymer with its polymerization rate varied depending on location within the polymer (hereinafter referred to as polymerization rate-distributed polymer) can be obtained by impregnating a polymerizable monomer into a substrate with a concentration gradient, followed by polymerization.
  • the impregnated monomer concentration shows a diffusion distribution having the highest concentration in the periphery of the substrate, and it is difficult to provide a highly concentrated region at a prescribed position, e.g., inside the substrate. That is, the process has a narrow freedom of polymerization rate distribution.
  • One object of the present invention is to provide a process for producing a polymerization or crosslinking rate-distributed article, which process is excellent in controllability of distribution mode, freedom in designing a distribution mode, fineness of the pattern, precision of distribution, and suitability to mass production.
  • Another object of the present invention is to provide a process for producing a lens, a lens array or a waveguide by application of the above process.
  • the above objects of the present invention are accomplished by (1) a process for producing a polymer or a crosslinked article comprising irradiating a matrix base containing a photo-reactive substance with laser light having an uneven distribution of intensity to form a region in which polymerization rate or crosslinking rate is varied, (2) a process for producing a lens or a lens array comprising irradiating laser light having an uneven distribution of intensity on at least one site of a transparent matrix base containing a photo-reactive substance to form at least one region in which a polymerization rate or a crosslinking rate is varied, and (3) a process for producing a waveguide comprising patternwise irradiating laser light having uneven distribution of intensity on a transparent matrix base containing a photo-reactive substance having a refractive index controlling activity to form a region in which the polymerization rate or the crosslinking rate is varied.
  • irradiation of a photo-reactive substance with laser light having an uneven distribution of intensity results in differences in polymerization rate or crosslinking rate in proportion to the differences in amount of reaction based on the light intensity distribution to thereby provide at least one region having uneven distribution of polymerization rate or crosslinking rate.
  • light intensity distribution of laser light usually shows a Gaussian distribution
  • the polymerization rate or crosslinking rate in the irradiated region continuously varies in accordance with the Gaussian distribution.
  • the region in which a polymerization rate or crosslinking rate is continuously varied will be hereinafter simply referred to as a distribution region.
  • the mode of distribution of the polymerization rate or crosslinking rate can be controlled arbitrarily by adjustment of the irradiation dose or scanning conditions of laser light.
  • the irradiation dose can be adjusted by irradiation time, the position of a laser beam, the diameter of a laser beam, and the like. Therefore, the process of the present invention is suitable for formation of a distribution region on an industrial scale. Since distribution regions having a standardized form can regularly be formed with ease, microlenses, etc., can be arrayed with good precision at a high density.
  • FIG. 1 illustrates a schematic view of an apparatus which can be used to conduct the present invention.
  • FIG. 2 is a graph showing refractive index distribution of the polymers and crosslinked article obtained in Examples 1, 2 and 4 and Comparative Examples 1 and 2.
  • FIG. 3 is a graph showing thickness changes in the polymers obtained in Example 3 and Comparative Example 3.
  • FIG. 4 is a perspective view of a lens with a partial cut area.
  • FIG. 5 is a perspective view of a lens array plate with a partial cut area.
  • FIG. 6 is a graph showing refractive index distribution of the lens array plates obtained in Examples 5 to 7 and Comparative Example 4.
  • FIG. 7 is a cross section of a lens.
  • FIG. 8 is a cross section of a lens array plate.
  • FIG. 9 is a graph showing the shape of lenses obtained in Examples 8, 10 and 11 and Comparative Example 5.
  • FIG. 10 is a graph showing the shape of the lens array obtained in Example 9.
  • FIG. 11 is a perspective view of a lens array plate prepared in Example 12 with a partial cut area thereof.
  • FIGS. 12 through 15 each is a plane view of an optical mask.
  • FIGS. 16 through 18 each shows refractive index distribution of a single lens of the lens array plate obtained in Example 12 or Comparative Example 6 or 7, respectively.
  • FIG. 19 is a perspective view of a waveguide.
  • FIG. 20 is a perspective view of a waveguide array.
  • FIGS. 21 and 22 each is a graph of refractive index distribution of the waveguides obtained in Example 13 and Comparative Example 8, respectively.
  • photo-reactive substance includes a photopolymerizable substance and a photo-crosslinkable substance.
  • the photo-reactive substance which can be used in the present invention is not particularly limited.
  • the object to be irradiated with laser light comprises a combination of a transparent matrix and at least one photopolymerizable substance or photo-crosslinkable substance; the photopolymerizable or photo-crosslinkable substance may undergo photo-reaction on irradiation with laser light.
  • the matrix materials which can be used in the present invention include a monomer, an oligomer, a resin, glass or any other inorganic substance.
  • the shape, size, thickness and the like of the object may be selected arbitrarily.
  • the surface properties of the object are also arbitrary, the object preferably has a smooth surface in order to prevent scattering of irradiated light so as to improve controllability of the reaction rate.
  • the object does not need to be a solid at the stage of irradiation and may be an object which can be solidified by an appropriate treatment after irradiation, such as a heat treatment or exposure to light.
  • Suitable objects of laser light irradiation include those composed of a matrix selected from a photopolymerizable or photo-crosslinkable polymer, glass or inorganic crystal or a composite material thereof and a non-photopolymerizable or non-photo-crosslinkable polymer, glass or inorganic crystal or a composite material thereof containing a photo-reactive substance, such as a photopolymerizable or photo-crosslinkable monomer or a mixture thereof or photosensitive glass, etc.
  • the object may contain a photo-reaction initiator or a photosensitizer.
  • Usable photo-reaction initiators include photopolymerizable or photo-crosslinkable substances and radical initiators.
  • the object of laser light irradiation may be a transparent sheet comprising a matrix base containing at least one photo-reactive substance.
  • the matrix bases used include those showing transparency to the light irradiated, such as polyolefins, various synthetic rubbers, polyvinyl chloride, polyester, polyamide, cellulose derivatives, polyvinyl alcohol, polyacrylates, polymethacrylates, polyurethane, polyurethane acrylate, and epoxy acrylate.
  • the photo-reactive substances incorporated into the matrix base include substances which undergo a reaction, such as polymerization, curing, addition or combination, among themselves or via a matrix upon being irradiated with laser light to provide a polymerized structure or a crosslinked structure based on the reaction mode of themselves or with a matrix.
  • the photo-reactive substances include photopolymerizable monomers, e.g., tribromophenoxyethyl acrylate and trifluoroethyl acrylate, and photo-crosslinkable monomers having at least two photo-reacting functional groups, e.g., divinylbenzene.
  • Physical properties of the resulting irradiation product such as a refractive index, can appropriately be controlled according to the kind of the photo-reactive substance used.
  • Formation of the photo-reactive substance-containing matrix base is not particularly restricted.
  • a base-forming polymer, etc. and a photo-reactive substance are mixed with or without a solvent, and the mixture is cast to obtain a sheet; or a photo-reactive substance with or without a solvent is impregnated into a previously formed matrix base.
  • the amount of a photo-reactive substance to be incorporated into a matrix base is appropriately selected according to a desired rate of polymerization or crosslinking or a desired distribution thereof. In general, it is used in an amount of not more than 200 parts by weight, and particularly not more than 100 parts by weight, per 100 parts by weight of a matrix base. While not limiting, the thickness of the matrix base is usually from 1 ⁇ m to 50 cm.
  • Laser light irradiated onto the thus prepared object should have a distribution of intensity so as to form a distribution region having distribution of a polymerization rate or crosslinking rate corresponding to the distribution of light intensity.
  • the object either before or after the irradiation may be subjected to an appropriate treatment, such as development, heating, pre-exposure, post-exposure, and a solvent treatment.
  • Laser light irradiation can be carried out by means of an appropriate laser oscillator according to the reactive wavelength of the photo-reactive substances present in the object, i.e., a photopolymerizable or photo-crosslinkable substance, a photo-reaction initiator, and a photosensitizer.
  • a laser oscillator capable of forming a beam having a circular section and having a zero-order or first-order Gaussian distribution of intensity is preferred.
  • laser oscillators generally employed include those emitting laser light of relatively short wavelength, such as an excimer laser, an argon laser, and a helium-cadmium laser.
  • a helium-neon laser having a relatively long oscillation wavelength may be used.
  • a laser of longer wavelength e.g., a YAG laser, if necessary with the wavelength converted to third harmonics, etc., may also be employed.
  • an argon laser, a helium-cadmium laser or the like is preferably used.
  • FIG. 1 an apparatus for conducting the process of the present invention, which comprises laser oscillator 1, shutter 2, condensing element 3 (e.g., lenses, mirrors, filters, etc.), and optical system 4 for scanning.
  • Laser light shown by an arrow
  • condensing element 3 e.g., lenses, mirrors, filters, etc.
  • optical system 4 for scanning.
  • Laser light shown by an arrow
  • Shutter 2 is to control the passage of laser light to condensing element 3. It is preferable for control of the photo-reaction rate that shutter 2 be controlled together with condensing element 3 and/or optical system 4.
  • the control of shutter 2 can easily be effected with equipment of personal computer level.
  • Distribution of the polymerization rate or crosslinking rate can be controlled by, for example, adjustment of the irradiation time, the intensity of the light irradiated, the position or the size of the laser light beam, extinction by means of a filter or a transmission-distributed optical mask, or control of the scanning passageway or speed.
  • a distribution region in which the polymerization rate or crosslinking rate continuously changes depicting a smooth curve based on a Gaussian distribution, etc. may be formed by irradiation for a prescribed time without scanning.
  • an arbitrary distribution region may be formed by scanning the laser light. While the diameter of the irradiating beam can be decided appropriately, it is usually from about 0.01 to 200 mm.
  • a region in which a polymerization rate or crosslinking rate continuously changes along the scanning passageway is formed.
  • the amount of irradiation per unit distance is adjusted by controlling the degree of condensation or the scanning speed to thereby control the width of the region formed.
  • the region is usually formed on both sides of the scanning passageway. Accordingly, crossing or superposing scanning passageways forms a portion having a different reaction rate from the other scanned portions.
  • the form of the distribution region formed by laser light irradiation is not limited. That is, the distribution may exist in either the whole or a part of an object, and a plurality of distribution regions may be formed to provide an array of lenses.
  • the form and surface conditions of the distribution region are not limited, either. Where a plurality of distribution regions are formed, the shape, the position, and the number of the regions are arbitrary. The mode or pattern of distribution in the region can be decided appropriately depending on the end use.
  • a lens or lens array having an excellent uniformity in a thickness direction can be obtained.
  • any unreacted photo-reactive substance and the like remaining in the irradiated article may be removed if necessary by an appropriate means, for example, extraction with a solvent or vaporization by heating according to the substance removed. That is, the object either before or after the irradiation may be subjected to an appropriate treatment, such as development, heating, pre-exposure, post-exposure, and a solvent treatment.
  • the process of the present invention is applicable to various purposes, such as production of a refractive index-distributed lens or an array thereof, production of a waveguide or an array thereof, partial reinforcement of soft and frail materials, partial softening of brittle materials, improvement of sliding resistance of sliding parts, and production of materials with a gradient function.
  • a lens or a lens array can be produced by irradiating laser light having a distribution of intensity on one or more sites of a transparent matrix base containing a photo-reactive substance to form one or more regions having a varying polymerization rate or crosslinking rate.
  • a refractive index-distributed lens or an array thereof can be obtained by choosing a photo-reactive substance having a refractive index regulating activity.
  • a lens plate or a lens array plate comprising a transparent support layer having thereon or therein one or more convex lens regions comprising a photopolymer can be produced by forming one or more regions having distribution of polymerization rate by laser light irradiation and then removing the unreacted photopolymerizable substance.
  • a waveguide can be produced by patternwise irradiating a transparent matrix base containing a photo-reactive substance having a refractive index regulating activity to form a distribution region having a varying polymerization rate or crosslinking rate.
  • a refractive index-distributed lens or an array thereof when the refractive index is distributed to have a quadratic distribution curve with its apex being in the center of the lens, there is provided a flat lens.
  • the lens having its maximum refractive index in the center thereof serves as a convex lens
  • the lens having its minimum refractive index in the center thereof serves as a concave lens.
  • a single lens or a unit lens constituting a lens array usually has a diameter of from 0.01 to 200 mm.
  • the process of the present invention can provide a distribution region in which the polymerization rate or a crosslinking rate continuously changes, the process can be applied to modification of a part of an article, such as reinforcement or softening without causing drastic change in the composition to be modified in favor of dispersion of a stress.
  • the process is capable of forming a distribution region over a length of from 1 ⁇ m to 50 cm or, if desired, even greater, it is also applicable to addition of functions, such as sliding resistance, or formation of gradation of a function without making a distinct boundary and without requiring any joint means.
  • a bifunctional urethane acrylate-based cured sheet having a thickness of 500 ⁇ m (“UNIDIC V-4220” produced by Dainippon Ink and Chemicals, Inc.) was impregnated with a solution of 10 parts of tribromophenoxyethyl acrylate and 0.1 part of a photo-reaction initiator ("IRGACURE 651" produced by Ciba Geigy) in 10 parts of chloroform, and the chloroform was removed by drying at 50° C. in a dark place.
  • the impregnated sheet was irradiated with a laser beam having a diameter of 1.2 mm emitted from a helium-cadmium laser (output: 7 mW) for 2 ms to cause polymerization of tribromophenoxyethyl acrylate.
  • the sheet was then immersed in methanol to remove unreacted tribromophenoxyethyl acrylate to obtain a polymerization rate-distributed polymer.
  • a polymerization rate-distributed polymer was obtained in the same manner as in Example 1, except for changing the beam diameter to 3 mm and the irradiation time to 12 seconds.
  • a solution consisting of 100 parts of methyl methacrylate and 0.1 part of IRGACURE 651 was put in a container having been treated with a release agent.
  • the contents were irradiated with laser light in a nitrogen atmosphere under the same conditions as in Example 1 and then heated to remove the unreacted monomer to obtain a polymerization rate-distributed polymer.
  • An impregnated sheet prepared in the same manner as in Example 1 was irradiated with ultraviolet light through an optical mask having a 1 mm wide opening. Unreacted tribromophenoxyethyl acrylate was extracted from the irradiated sheet to obtain a polymer.
  • Both sides of a bifunctional urethane acrylate-based cured sheet having a thickness of 500 ⁇ m were plated with nickel while leaving a circle having a diameter of 1 mm unplated on each side.
  • the Ni-plated sheet was soaked in the same monomer solution as used in Example 1. Immediately after being taken out of the solution, the impregnated sheet was irradiated with ultraviolet light. The Ni-plate layer was removed, and unreacted tribromophenoxyethyl acrylate was removed by extraction to obtain a polymer.
  • a polymer was prepared in the same manner as in Example 3, except that the same monomer solution as used in Example 1 was irradiated with ultraviolet light through an optical mask having a 1 mm wide opening.
  • Each of the polymers and crosslinked article obtained in the above-described Examples and Comparative Examples was evaluated by measuring the refractive index distribution with a differential interference microscope (manufactured by CARL ZEISS JENA; hereinafter the same).
  • a refractive index appears as an average of the refractive index of the polymer or crosslinked article and that of the matrix resin based on their concentration ratio. From the average refractive index is decided the polymerization rate or crosslinking rate distribution as a concentration distribution of the polymer or crosslinked article.
  • Examples 1, 2, and 4 and Comparative Examples 1 and 2 are shown in FIG. 2.
  • the refractive index changes substantially continuously, revealing a distribution region in which the polymerization rate or crosslinking rate continuously changes. It is also seen from the results of Examples 1 and 2 that the area having a distribution can be controlled by adjusting the area to be irradiated with laser light. To the contrary, the change in refractive index in Comparative Examples 1 and 2 is stepwise, indicating that there was formed no substantial distribution of polymerization rate.
  • Example 3 depicts a smooth convex curve corresponding to a Gaussian distribution, revealing a distribution region in which the polymerization rate continuously changes.
  • the change in thickness observed in Comparative Example 3 is a result of disturbance due to running of the resin during removal of the unreacted monomer. Such a change in thickness is irregular and uncontrollable.
  • a lens array plate was prepared in the same manner as in Example 5, except for replacing tribromophenoxyethyl acrylate with trifluoroethyl acrylate (refractive index-reducing type; refractive index: 1.3).
  • a bifunctional urethane acrylate-based cured sheet having a thickness of 500 ⁇ m (“UNIDIC 15-829" produced by Dainippon Ink and Chemicals, Inc.) was impregnated with a solution of 10 parts of tribromophenoxyethyl acrylate and 0.1 part of IRGACURE 651 in 10 parts of chloroform. The chloroform was removed from the impregnated sheet in a dark place, and the sheet was then irradiated with laser light in the same manner as in Example 5 to obtain a lens array plate.
  • Example 7 The same impregnated sheet as prepared in Example 7 was irradiated with ultraviolet light through an optical mask having openings having a diameter of 500 ⁇ m at intervals of 800 ⁇ m in a closest packing mode. Unreacted tribromophenoxyethyl acrylate was removed by extraction to obtain a lens array plate.
  • the lens array plates obtained in Examples 5 to 7 and Comparative Example 4 were cut and the cross-sections thereof were observed. As a result, the lens array plates of Examples 5 to 7 had a good uniformity in the thickness direction, but the lens array plate of Comparative Example 4 had an ununiformity in the thickness direction.
  • each unit lens of Examples 5 and 7 exhibited satisfactory optical characteristics of a convex lens
  • each unit lens of Example 6 exhibited satisfactory optical characteristics of a concave lens.
  • the product of Comparative Example 4 showed no lens function.
  • a 50 ⁇ m thick transparent film comprising a urethane acrylate-based polymer was impregnated with a solution of 1 part of tribromophenoxyethyl acrylate (refractive index: 1.56) and 1 part of IRGACURE 651 in 1 part of chloroform.
  • the impregnated film was irradiated with a helium-cadmium laser beam of zero-order lateral oscillation mode (output: 4.2 mW) for 2 seconds.
  • the irradiated film was immersed in methanol for 6 hours to remove unreacted tribromophenoxyethyl acrylate to obtain a lens plate having a cross section shown in FIG. 7
  • a lens array plate having a cross section shown in FIG. 8 was obtained in the same manner as in Example 8, except that the laser beam was irradiated on 16 spots (4 ⁇ 4) at a center-to-center pitch of 1.1 mm.
  • a lens plate of FIG. 7 was obtained in the same manner as in Example 8, except for changing the irradiation time to 6 seconds.
  • a lens plate was obtained in the same manner as in Example 8, except that after irradiation for the first 1 second, the beam diameter was reduced to half in the next 1 second.
  • a lens plate was prepared in the same manner as in Example 8, except that the impregnated film was irradiated with ultraviolet light for 20 seconds through an optical mask having an opening of 1.0 mm in diameter.
  • Example 9 Thickness change of each of the lens plates obtained in Examples 8, 10, and 11 and Comparative Example 5 and the lens array plate obtained in Example 9 was examined with a surface roughness meter. The results of Example 9 are shown in FIG. 10, and the others in FIG. 9. In FIGS. 9 and 10, the base line of height (0 mm) is the surface of the transparent film support, and the base line of distance (0 mm) is one end of the formed convex lens region.
  • Example 8 shows convexity having a quadratic surface
  • Example 10 has convexity with a plateau
  • Example 11 has a double curved surface.
  • no curved surface is formed in Comparative Example 5.
  • the lens characteristics of each lens were examined.
  • the lens of Example 8 displayed satisfactory convex lens characteristics having a small spherical aberration.
  • the lens of Example 10 exhibited characteristics of an aspherical lens.
  • the lens of Example 11 has satisfactory characteristics of a double focal point lens. To the contrary, no lens function was exhibited in Comparative Example 5.
  • the plate of Example 9 has 4 ⁇ 4 convexities with a quadratic surface each having a diameter of about 1 mm at small intervals of about 0.2 mm. All the unit lenses were regular in shape, i.e., diameter, height, etc. Further, by conducting separate experiments, it was confirmed that various lens array plates can easily be produced by making alterations of the irradiation pitch, the diameter of the laser light beam or the irradiation time.
  • a lens array plate was prepared in the same manner as in Example 12, except for using no optical mask.
  • a polystyrene rod was immersed with a solution of 100 parts of methyl methacrylate and 1 part of benzophenone, and the monomer was polymerized to obtain a refractive index-distributed rod.
  • the resulting rod was drawn into fiber while heating, followed by cutting.
  • the cut fibers were bundled and adhered together with an epoxy resin under pressure. Both sides of the fiber bundle were cut and scratch polished to obtain a lens array plate.
  • the refractive index distribution in a unit lens of the lens array plate obtained in Example 12 or Comparative Example 6 or 7 was determined with a differential interference microscope. The results obtained are shown in FIGS. 16, 17, and 18, respectively, in which a difference of refractive index from that of the center taken as a standard (0) is depicted as a contour line. In each case, the length of the horizontal line connecting two points on the contour line of the refractive index difference of -0.03 and passing the center was about 1 mm.
  • the refractive index of a unit lens of Example 12 changed substantially continuously.
  • the aperture was about 95%, which is much greater than that obtained when circular lenses are arrayed in a closest packing mode (78.5%).
  • the plurality of lens regions formed each had a substantially regular hexagonal shape, the outer edges of which were shared by neighboring regions.
  • the refractive index distribution in each region showed nearly circular and concentric contour lines.
  • Comparative Example 6 On the other hand, a large proportion in a unit lens showed no distribution of a refractive index, and the aperture was about 70%. In Comparative Example 7, although an aperture of about 90% was obtained, each unit lens had refractive index distribution shown by hexagonal contour lines and was poor in transmission efficiency.
  • a waveguide array shown in FIG. 20 was obtained in the same manner as in Example 13, except that the laser beam was scanned along two parallel tracks at a distance of 10 mm to form two parallel refractive index-distributed waveguides.
  • a 50 ⁇ m thick bifunctional urethane acrylate-based cured sheet was impregnated with a solution of 10 part of tribromophenoxyethyl acrylate and 0.1 part of IRGACURE 651 in 10 parts of chloroform. After removing chloroform in a dark place, the impregnated sheet was irradiated with laser light in the same manner as in Example 13 to obtain a refractive index-distributed waveguide.
  • Laser light was linearly scanned on the same impregnated sheet as used in Example 15 in the same manner as in Example 15, then turned in a U-form at a curvature radius of 50 mm, and further linearly scanned to obtain a refractive index-distributed waveguide having a U-form.
  • Example 15 The same impregnated sheet as prepared in Example 15 was irradiated with ultraviolet light through an optical mask having 10 ⁇ m wide openings at intervals decreasing from 100 ⁇ m to 15 ⁇ m. Unrelated tribromophenoxyethyl acrylate was removed by extraction to obtain a waveguide array.
  • Example 13 to 16 and Comparative Example 8 were evaluated in terms of refractive index distribution in the width direction by means of a differential interference microscope.
  • the results of Example 13 and Comparative Example 8 are shown in FIGS. 21 and 22, respectively.
  • the refractive index changes in a half side of the waveguide are shown, taking the refractive index at the center as a standard (0).
  • FIG. 21 reveals a continuous change of refractive index within a waveguiding width of 49 ⁇ m.
  • the waveguide had a width of 1250 ⁇ m in which the refractive index changed stepwise.
  • the transmission zone of the waveguide was 260 MHz in Example 13 and 40 MHz in Comparative Example 8. Further, helium-neon laser light was passed through the waveguide to determine the transmission loss. As a result, the transmission loss was 1.7 dB/cm in Example 13 and 3.6 dB/cm in Comparative Example 8.
  • Example 14 the transmission zone of each waveguide of the waveguide array obtained in Example 14 was 260 MHz, the same as in Example 13, and that of Examples 15 and 16 was 270 MHz and 210 MHz, respectively.
  • the transmission loss in Example 15 was 1.7 dB/cm, the same as in Example 13.
  • a waveguide having a width of 20 ⁇ m could be formed by condensing the beam diameter of laser light.
  • a polymerization rate-distributed polymer or a crosslinking rate-distributed article can be formed effectively by irradiation using laser light.
  • the process of the present invention is suitable for mass production.
  • An arbitrary distribution pattern can be designed and formed under good control, and distribution regions having a fine shape can be formed with excellent precision.
  • a plurality of distribution regions having a regular shape can be formed at a high density with high precision.

Abstract

A process for producing a polymer or a crosslinked article having a region in which the polymerization rate or crosslinking rate is varied is disclosed, comprising irradiating a photopolymerizable substance or photo-crosslinkable substance with laser light having an uneven distribution of intensity. The process is suitable for mass production of polymerization rate- or crosslinking rate-distributed articles. An arbitrary distribution pattern can be designed and formed under good control, and distribution regions having a fine shape can be formed with excellent precision. A plurality of distribution regions having a regular shape can be formed at a high density with high precision.

Description

This is a Continuation of application Ser. No. 08/511,913 filed Aug. 7, 1995, which is a Continuation of application Ser. No. 08/077,036 filed Jun. 16, 1993.
FIELD OF THE INVENTION
This invention relates to a process for producing a polymer having an uneven distribution of a polymerization rate or a crosslinked article having an uneven distribution of a crosslinking rate. The process is applicable to formation of microlenses having an uneven distribution of refractive index.
BACKGROUND OF THE INVENTION
It is known that a polymer having an uneven distribution of a polymerization rate, i.e., a polymer with its polymerization rate varied depending on location within the polymer (hereinafter referred to as polymerization rate-distributed polymer) can be obtained by impregnating a polymerizable monomer into a substrate with a concentration gradient, followed by polymerization. According to this technique, however, the impregnated monomer concentration shows a diffusion distribution having the highest concentration in the periphery of the substrate, and it is difficult to provide a highly concentrated region at a prescribed position, e.g., inside the substrate. That is, the process has a narrow freedom of polymerization rate distribution.
A modification of the above-described process has been proposed, in which part of the surface of a substrate is covered with an impermeable mask to control the site where a polymerizable monomer is impregnated. However, this modification makes no difference in terms of diffusion distribution from the site of impregnation toward the surroundings, and the freedom of polymerization rate distribution is still limited. Therefore, whichever process one may choose, a concentration distribution is determined by the type of substrate and polymerizable monomer and environmental conditions. The processes are difficult to control, freedom of the possible pattern of polymerization rate distribution is extremely narrow, and there are difficulties in controlling distribution mode and in freely designing polymerization rate-distributed regions.
On the other hand, it has been proposed to expose a photopolymerizable compound or a photo-crosslinkable compound to light through an optical mask having a binary pattern having openings at varied intervals to produce a polymerization rate-distributed polymer or a crosslinked article with its crosslinking rate unevenly distributed (hereinafter referred to as a crosslinking rate-distributed article) based on the areas of the irradiated portions (exposure portions) and unirradiated portions (non-exposure portions). However, this process is disadvantageous in that preparation of such an optical mask requires much time and labor, an optical mask must be prepared for every pattern of proposed distribution, and incident light is diffracted by the optical mask, resulting in poor reproduction precision of distribution. In particular, the diffraction of light becomes greater as the pattern is made finer. Therefore, the process lacks reproducibility in forming fine regions needing highly precise control as in the formation of microlenses.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a process for producing a polymerization or crosslinking rate-distributed article, which process is excellent in controllability of distribution mode, freedom in designing a distribution mode, fineness of the pattern, precision of distribution, and suitability to mass production.
Another object of the present invention is to provide a process for producing a lens, a lens array or a waveguide by application of the above process.
The above objects of the present invention are accomplished by (1) a process for producing a polymer or a crosslinked article comprising irradiating a matrix base containing a photo-reactive substance with laser light having an uneven distribution of intensity to form a region in which polymerization rate or crosslinking rate is varied, (2) a process for producing a lens or a lens array comprising irradiating laser light having an uneven distribution of intensity on at least one site of a transparent matrix base containing a photo-reactive substance to form at least one region in which a polymerization rate or a crosslinking rate is varied, and (3) a process for producing a waveguide comprising patternwise irradiating laser light having uneven distribution of intensity on a transparent matrix base containing a photo-reactive substance having a refractive index controlling activity to form a region in which the polymerization rate or the crosslinking rate is varied.
According to the present invention, irradiation of a photo-reactive substance with laser light having an uneven distribution of intensity results in differences in polymerization rate or crosslinking rate in proportion to the differences in amount of reaction based on the light intensity distribution to thereby provide at least one region having uneven distribution of polymerization rate or crosslinking rate. Since light intensity distribution of laser light usually shows a Gaussian distribution, the polymerization rate or crosslinking rate in the irradiated region continuously varies in accordance with the Gaussian distribution. The region in which a polymerization rate or crosslinking rate is continuously varied will be hereinafter simply referred to as a distribution region.
The mode of distribution of the polymerization rate or crosslinking rate can be controlled arbitrarily by adjustment of the irradiation dose or scanning conditions of laser light. The irradiation dose can be adjusted by irradiation time, the position of a laser beam, the diameter of a laser beam, and the like. Therefore, the process of the present invention is suitable for formation of a distribution region on an industrial scale. Since distribution regions having a standardized form can regularly be formed with ease, microlenses, etc., can be arrayed with good precision at a high density.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a schematic view of an apparatus which can be used to conduct the present invention.
FIG. 2 is a graph showing refractive index distribution of the polymers and crosslinked article obtained in Examples 1, 2 and 4 and Comparative Examples 1 and 2.
FIG. 3 is a graph showing thickness changes in the polymers obtained in Example 3 and Comparative Example 3.
FIG. 4 is a perspective view of a lens with a partial cut area.
FIG. 5 is a perspective view of a lens array plate with a partial cut area.
FIG. 6 is a graph showing refractive index distribution of the lens array plates obtained in Examples 5 to 7 and Comparative Example 4.
FIG. 7 is a cross section of a lens.
FIG. 8 is a cross section of a lens array plate.
FIG. 9 is a graph showing the shape of lenses obtained in Examples 8, 10 and 11 and Comparative Example 5.
FIG. 10 is a graph showing the shape of the lens array obtained in Example 9.
FIG. 11 is a perspective view of a lens array plate prepared in Example 12 with a partial cut area thereof.
FIGS. 12 through 15 each is a plane view of an optical mask.
FIGS. 16 through 18 each shows refractive index distribution of a single lens of the lens array plate obtained in Example 12 or Comparative Example 6 or 7, respectively.
FIG. 19 is a perspective view of a waveguide.
FIG. 20 is a perspective view of a waveguide array.
FIGS. 21 and 22 each is a graph of refractive index distribution of the waveguides obtained in Example 13 and Comparative Example 8, respectively.
DETAILED DESCRIPTION OF THE INVENTION
The terminology "photo-reactive substance" as used herein includes a photopolymerizable substance and a photo-crosslinkable substance. The photo-reactive substance which can be used in the present invention is not particularly limited.
The object to be irradiated with laser light comprises a combination of a transparent matrix and at least one photopolymerizable substance or photo-crosslinkable substance; the photopolymerizable or photo-crosslinkable substance may undergo photo-reaction on irradiation with laser light. The matrix materials which can be used in the present invention include a monomer, an oligomer, a resin, glass or any other inorganic substance. The shape, size, thickness and the like of the object may be selected arbitrarily. While the surface properties of the object are also arbitrary, the object preferably has a smooth surface in order to prevent scattering of irradiated light so as to improve controllability of the reaction rate. The object does not need to be a solid at the stage of irradiation and may be an object which can be solidified by an appropriate treatment after irradiation, such as a heat treatment or exposure to light.
Suitable objects of laser light irradiation include those composed of a matrix selected from a photopolymerizable or photo-crosslinkable polymer, glass or inorganic crystal or a composite material thereof and a non-photopolymerizable or non-photo-crosslinkable polymer, glass or inorganic crystal or a composite material thereof containing a photo-reactive substance, such as a photopolymerizable or photo-crosslinkable monomer or a mixture thereof or photosensitive glass, etc. If desired, the object may contain a photo-reaction initiator or a photosensitizer. Usable photo-reaction initiators include photopolymerizable or photo-crosslinkable substances and radical initiators.
The object of laser light irradiation may be a transparent sheet comprising a matrix base containing at least one photo-reactive substance. The matrix bases used include those showing transparency to the light irradiated, such as polyolefins, various synthetic rubbers, polyvinyl chloride, polyester, polyamide, cellulose derivatives, polyvinyl alcohol, polyacrylates, polymethacrylates, polyurethane, polyurethane acrylate, and epoxy acrylate.
The photo-reactive substances incorporated into the matrix base include substances which undergo a reaction, such as polymerization, curing, addition or combination, among themselves or via a matrix upon being irradiated with laser light to provide a polymerized structure or a crosslinked structure based on the reaction mode of themselves or with a matrix. Examples of the photo-reactive substances include photopolymerizable monomers, e.g., tribromophenoxyethyl acrylate and trifluoroethyl acrylate, and photo-crosslinkable monomers having at least two photo-reacting functional groups, e.g., divinylbenzene. Physical properties of the resulting irradiation product, such as a refractive index, can appropriately be controlled according to the kind of the photo-reactive substance used.
Formation of the photo-reactive substance-containing matrix base is not particularly restricted. For example, a base-forming polymer, etc. and a photo-reactive substance are mixed with or without a solvent, and the mixture is cast to obtain a sheet; or a photo-reactive substance with or without a solvent is impregnated into a previously formed matrix base. The amount of a photo-reactive substance to be incorporated into a matrix base is appropriately selected according to a desired rate of polymerization or crosslinking or a desired distribution thereof. In general, it is used in an amount of not more than 200 parts by weight, and particularly not more than 100 parts by weight, per 100 parts by weight of a matrix base. While not limiting, the thickness of the matrix base is usually from 1 μm to 50 cm.
Laser light irradiated onto the thus prepared object should have a distribution of intensity so as to form a distribution region having distribution of a polymerization rate or crosslinking rate corresponding to the distribution of light intensity. If desired, the object either before or after the irradiation may be subjected to an appropriate treatment, such as development, heating, pre-exposure, post-exposure, and a solvent treatment.
Laser light irradiation can be carried out by means of an appropriate laser oscillator according to the reactive wavelength of the photo-reactive substances present in the object, i.e., a photopolymerizable or photo-crosslinkable substance, a photo-reaction initiator, and a photosensitizer. A laser oscillator capable of forming a beam having a circular section and having a zero-order or first-order Gaussian distribution of intensity is preferred.
Examples of laser oscillators generally employed include those emitting laser light of relatively short wavelength, such as an excimer laser, an argon laser, and a helium-cadmium laser. Depending on the photo-reaction initiator or photosensitizer used a helium-neon laser having a relatively long oscillation wavelength may be used. Further, a laser of longer wavelength, e.g., a YAG laser, if necessary with the wavelength converted to third harmonics, etc., may also be employed. Of those, an argon laser, a helium-cadmium laser or the like is preferably used.
In FIG. 1 is shown an apparatus for conducting the process of the present invention, which comprises laser oscillator 1, shutter 2, condensing element 3 (e.g., lenses, mirrors, filters, etc.), and optical system 4 for scanning. Laser light (shown by an arrow) from laser oscillator 1 is condensed through condensing element 3 into a beam of adjusted size, which is then reflected on optical system 4 to the direction of object 5. The position of irradiation and the track of scanning are decided by controlling optical system 4. Shutter 2 is to control the passage of laser light to condensing element 3. It is preferable for control of the photo-reaction rate that shutter 2 be controlled together with condensing element 3 and/or optical system 4. The control of shutter 2 can easily be effected with equipment of personal computer level.
Distribution of the polymerization rate or crosslinking rate can be controlled by, for example, adjustment of the irradiation time, the intensity of the light irradiated, the position or the size of the laser light beam, extinction by means of a filter or a transmission-distributed optical mask, or control of the scanning passageway or speed. In the present invention, a distribution region in which the polymerization rate or crosslinking rate continuously changes depicting a smooth curve based on a Gaussian distribution, etc., may be formed by irradiation for a prescribed time without scanning. Alternatively, an arbitrary distribution region may be formed by scanning the laser light. While the diameter of the irradiating beam can be decided appropriately, it is usually from about 0.01 to 200 mm.
Where the above-described scanning system is adopted, a region in which a polymerization rate or crosslinking rate continuously changes along the scanning passageway is formed. In this case, the amount of irradiation per unit distance is adjusted by controlling the degree of condensation or the scanning speed to thereby control the width of the region formed. The region is usually formed on both sides of the scanning passageway. Accordingly, crossing or superposing scanning passageways forms a portion having a different reaction rate from the other scanned portions.
The form of the distribution region formed by laser light irradiation is not limited. That is, the distribution may exist in either the whole or a part of an object, and a plurality of distribution regions may be formed to provide an array of lenses. The form and surface conditions of the distribution region are not limited, either. Where a plurality of distribution regions are formed, the shape, the position, and the number of the regions are arbitrary. The mode or pattern of distribution in the region can be decided appropriately depending on the end use.
Further, by selecting a laser having a high degree of parallelism, a lens or lens array having an excellent uniformity in a thickness direction can be obtained.
After the laser light irradiation, any unreacted photo-reactive substance and the like remaining in the irradiated article may be removed if necessary by an appropriate means, for example, extraction with a solvent or vaporization by heating according to the substance removed. That is, the object either before or after the irradiation may be subjected to an appropriate treatment, such as development, heating, pre-exposure, post-exposure, and a solvent treatment.
The process of the present invention is applicable to various purposes, such as production of a refractive index-distributed lens or an array thereof, production of a waveguide or an array thereof, partial reinforcement of soft and frail materials, partial softening of brittle materials, improvement of sliding resistance of sliding parts, and production of materials with a gradient function.
More specifically, a lens or a lens array can be produced by irradiating laser light having a distribution of intensity on one or more sites of a transparent matrix base containing a photo-reactive substance to form one or more regions having a varying polymerization rate or crosslinking rate. In this case, a refractive index-distributed lens or an array thereof can be obtained by choosing a photo-reactive substance having a refractive index regulating activity.
A lens plate or a lens array plate comprising a transparent support layer having thereon or therein one or more convex lens regions comprising a photopolymer can be produced by forming one or more regions having distribution of polymerization rate by laser light irradiation and then removing the unreacted photopolymerizable substance.
In the above-described process for producing a lens array, use of an optical mask having polygonal openings results in production of a lens array plate comprising a transparent support layer having a plurality of refractive index-distributed lens regions whose outer edge has a polygonal shape.
A waveguide can be produced by patternwise irradiating a transparent matrix base containing a photo-reactive substance having a refractive index regulating activity to form a distribution region having a varying polymerization rate or crosslinking rate.
In the production of a refractive index-distributed lens or an array thereof, when the refractive index is distributed to have a quadratic distribution curve with its apex being in the center of the lens, there is provided a flat lens. In this case, the lens having its maximum refractive index in the center thereof serves as a convex lens, while the lens having its minimum refractive index in the center thereof serves as a concave lens. A single lens or a unit lens constituting a lens array usually has a diameter of from 0.01 to 200 mm.
Since the process of the present invention can provide a distribution region in which the polymerization rate or a crosslinking rate continuously changes, the process can be applied to modification of a part of an article, such as reinforcement or softening without causing drastic change in the composition to be modified in favor of dispersion of a stress. In addition, since the process is capable of forming a distribution region over a length of from 1 μm to 50 cm or, if desired, even greater, it is also applicable to addition of functions, such as sliding resistance, or formation of gradation of a function without making a distinct boundary and without requiring any joint means.
The present invention will now be illustrated in greater detail by way of Examples, but it should be understood that the present invention is not construed as being limited thereto. All the parts are by weight unless otherwise indicated.
EXAMPLE 1
A bifunctional urethane acrylate-based cured sheet having a thickness of 500 μm ("UNIDIC V-4220" produced by Dainippon Ink and Chemicals, Inc.) was impregnated with a solution of 10 parts of tribromophenoxyethyl acrylate and 0.1 part of a photo-reaction initiator ("IRGACURE 651" produced by Ciba Geigy) in 10 parts of chloroform, and the chloroform was removed by drying at 50° C. in a dark place. The impregnated sheet was irradiated with a laser beam having a diameter of 1.2 mm emitted from a helium-cadmium laser (output: 7 mW) for 2 ms to cause polymerization of tribromophenoxyethyl acrylate. The sheet was then immersed in methanol to remove unreacted tribromophenoxyethyl acrylate to obtain a polymerization rate-distributed polymer.
EXAMPLE 2
A polymerization rate-distributed polymer was obtained in the same manner as in Example 1, except for changing the beam diameter to 3 mm and the irradiation time to 12 seconds.
EXAMPLE 3
A solution consisting of 100 parts of methyl methacrylate and 0.1 part of IRGACURE 651 was put in a container having been treated with a release agent. The contents were irradiated with laser light in a nitrogen atmosphere under the same conditions as in Example 1 and then heated to remove the unreacted monomer to obtain a polymerization rate-distributed polymer.
EXAMPLE 4
In 100 parts of chloroform were dissolved 100 parts of poly(vinylcarbazole) and 24 parts of camphorquinone, and the solvent was removed in a dark place. The residue was irradiated with laser light for 5 seconds in the same manner as in Example 1 and then immersed in toluene to remove unreacted camphorguinone, followed by drying to obtain a crosslinking rate-distributed article.
COMPARATIVE EXAMPLE 1
An impregnated sheet prepared in the same manner as in Example 1 was irradiated with ultraviolet light through an optical mask having a 1 mm wide opening. Unreacted tribromophenoxyethyl acrylate was extracted from the irradiated sheet to obtain a polymer.
COMPARATIVE EXAMPLE 2
Both sides of a bifunctional urethane acrylate-based cured sheet having a thickness of 500 μm were plated with nickel while leaving a circle having a diameter of 1 mm unplated on each side. The Ni-plated sheet was soaked in the same monomer solution as used in Example 1. Immediately after being taken out of the solution, the impregnated sheet was irradiated with ultraviolet light. The Ni-plate layer was removed, and unreacted tribromophenoxyethyl acrylate was removed by extraction to obtain a polymer.
COMPARATIVE EXAMPLE 3
A polymer was prepared in the same manner as in Example 3, except that the same monomer solution as used in Example 1 was irradiated with ultraviolet light through an optical mask having a 1 mm wide opening.
Each of the polymers and crosslinked article obtained in the above-described Examples and Comparative Examples was evaluated by measuring the refractive index distribution with a differential interference microscope (manufactured by CARL ZEISS JENA; hereinafter the same). A refractive index appears as an average of the refractive index of the polymer or crosslinked article and that of the matrix resin based on their concentration ratio. From the average refractive index is decided the polymerization rate or crosslinking rate distribution as a concentration distribution of the polymer or crosslinked article.
The results of Examples 1, 2, and 4 and Comparative Examples 1 and 2 are shown in FIG. 2. In Examples 1, 2, and 4, the refractive index changes substantially continuously, revealing a distribution region in which the polymerization rate or crosslinking rate continuously changes. It is also seen from the results of Examples 1 and 2 that the area having a distribution can be controlled by adjusting the area to be irradiated with laser light. To the contrary, the change in refractive index in Comparative Examples 1 and 2 is stepwise, indicating that there was formed no substantial distribution of polymerization rate.
On the other hand, the thickness change of the polymers obtained in Example 3 and Comparative Example 3, which indicates a polymerization rate distribution, was examined by measuring the surface roughness. The results obtained are shown in FIG. 3. As shown in FIG. 3, Example 3 depicts a smooth convex curve corresponding to a Gaussian distribution, revealing a distribution region in which the polymerization rate continuously changes. To the contrary, the change in thickness observed in Comparative Example 3 is a result of disturbance due to running of the resin during removal of the unreacted monomer. Such a change in thickness is irregular and uncontrollable.
EXAMPLE 5
Ten parts of poly(methyl acrylate) obtained by solution polymerization, 10 parts of tribromophenoxyethyl acrylate (refractive index-increasing type; refractive index: 1.56), 0.1 part of IRGACURE 651, and 20 parts of ethyl acetate were mixed, and the mixture was cast to obtain a 100 μm thick film. The cast film was scanned with an argon laser beam having a diameter of 500 μm for 100 ms per spot. The irradiated film was immersed in methanol to remove unreacted tribromophenoxyethyl acrylate to obtain a lens array plate. Each circular lens had a diameter of about 0.6 mm, and the pitch (center-to-center) of the lenses was about 0.62 mm.
EXAMPLE 6
A lens array plate was prepared in the same manner as in Example 5, except for replacing tribromophenoxyethyl acrylate with trifluoroethyl acrylate (refractive index-reducing type; refractive index: 1.3).
EXAMPLE 7
A bifunctional urethane acrylate-based cured sheet having a thickness of 500 μm ("UNIDIC 15-829" produced by Dainippon Ink and Chemicals, Inc.) was impregnated with a solution of 10 parts of tribromophenoxyethyl acrylate and 0.1 part of IRGACURE 651 in 10 parts of chloroform. The chloroform was removed from the impregnated sheet in a dark place, and the sheet was then irradiated with laser light in the same manner as in Example 5 to obtain a lens array plate.
COMPARATIVE EXAMPLE 4
The same impregnated sheet as prepared in Example 7 was irradiated with ultraviolet light through an optical mask having openings having a diameter of 500 μm at intervals of 800 μm in a closest packing mode. Unreacted tribromophenoxyethyl acrylate was removed by extraction to obtain a lens array plate.
The lens array plates obtained in Examples 5 to 7 and Comparative Example 4 were cut and the cross-sections thereof were observed. As a result, the lens array plates of Examples 5 to 7 had a good uniformity in the thickness direction, but the lens array plate of Comparative Example 4 had an ununiformity in the thickness direction.
The refractive index distribution in those lens array plates was determined by means of a differential interference microscope. The results obtained are shown in FIG. 6. It is seen from FIG. 6 that the refractive index in Examples 5 to 7 changes substantially continuously and is also similar to the quadratic distribution curve, whereas the refractive index change in Comparative Example 4 is stepwise.
Further, light transmitted through each lens array plate was visually observed. As a result, each unit lens of Examples 5 and 7 exhibited satisfactory optical characteristics of a convex lens, and each unit lens of Example 6 exhibited satisfactory optical characteristics of a concave lens. To the contrary, the product of Comparative Example 4 showed no lens function.
EXAMPLE 8
A 50 μm thick transparent film comprising a urethane acrylate-based polymer was impregnated with a solution of 1 part of tribromophenoxyethyl acrylate (refractive index: 1.56) and 1 part of IRGACURE 651 in 1 part of chloroform. The impregnated film was irradiated with a helium-cadmium laser beam of zero-order lateral oscillation mode (output: 4.2 mW) for 2 seconds. The irradiated film was immersed in methanol for 6 hours to remove unreacted tribromophenoxyethyl acrylate to obtain a lens plate having a cross section shown in FIG. 7
EXAMPLE 9
A lens array plate having a cross section shown in FIG. 8 was obtained in the same manner as in Example 8, except that the laser beam was irradiated on 16 spots (4×4) at a center-to-center pitch of 1.1 mm.
EXAMPLE 10
A lens plate of FIG. 7 was obtained in the same manner as in Example 8, except for changing the irradiation time to 6 seconds.
EXAMPLE 11
A lens plate was obtained in the same manner as in Example 8, except that after irradiation for the first 1 second, the beam diameter was reduced to half in the next 1 second.
COMPARATIVE EXAMPLE 5
A lens plate was prepared in the same manner as in Example 8, except that the impregnated film was irradiated with ultraviolet light for 20 seconds through an optical mask having an opening of 1.0 mm in diameter.
Thickness change of each of the lens plates obtained in Examples 8, 10, and 11 and Comparative Example 5 and the lens array plate obtained in Example 9 was examined with a surface roughness meter. The results of Example 9 are shown in FIG. 10, and the others in FIG. 9. In FIGS. 9 and 10, the base line of height (0 mm) is the surface of the transparent film support, and the base line of distance (0 mm) is one end of the formed convex lens region.
It is apparent from FIG. 9 that the lens of Example 8 shows convexity having a quadratic surface, that of Example 10 has convexity with a plateau, and that of Example 11 has a double curved surface. On the other hand, no curved surface is formed in Comparative Example 5.
The lens characteristics of each lens were examined. The lens of Example 8 displayed satisfactory convex lens characteristics having a small spherical aberration. The lens of Example 10 exhibited characteristics of an aspherical lens. The lens of Example 11 has satisfactory characteristics of a double focal point lens. To the contrary, no lens function was exhibited in Comparative Example 5.
As shown in FIG. 10, the plate of Example 9 has 4×4 convexities with a quadratic surface each having a diameter of about 1 mm at small intervals of about 0.2 mm. All the unit lenses were regular in shape, i.e., diameter, height, etc. Further, by conducting separate experiments, it was confirmed that various lens array plates can easily be produced by making alterations of the irradiation pitch, the diameter of the laser light beam or the irradiation time.
EXAMPLE 12
Ten parts of poly(methyl acrylate) obtained by solution polymerization, 10 parts of tribromophenoxyethyl acrylate (refractive index: 1.56), 0.1 part of IRGACURE 651, and 20 parts of ethyl acetate were mixed, and the mixture was cast in a dark place to obtain a 100 μm thick film. The cast film was scanned with a helium-cadmium laser beam having a diameter of 1.2 mm for 2 seconds per spot through an optical mask having hexagonal openings so arrayed as to form distribution regions in a closest packing mode. The optical mask was set between shutter 2 and condensing element 3 with the center of the hexagonal opening being concentric with the center of the laser beam. The irradiated film was immersed in methanol to remove unreacted tribromophenoxyethyl acrylate to obtain a soft lens array plate shown in FIG. 11.
COMPARATIVE EXAMPLE 6
A lens array plate was prepared in the same manner as in Example 12, except for using no optical mask.
COMPARATIVE EXAMPLE 7
A polystyrene rod was immersed with a solution of 100 parts of methyl methacrylate and 1 part of benzophenone, and the monomer was polymerized to obtain a refractive index-distributed rod. The resulting rod was drawn into fiber while heating, followed by cutting. The cut fibers were bundled and adhered together with an epoxy resin under pressure. Both sides of the fiber bundle were cut and scratch polished to obtain a lens array plate.
The refractive index distribution in a unit lens of the lens array plate obtained in Example 12 or Comparative Example 6 or 7 was determined with a differential interference microscope. The results obtained are shown in FIGS. 16, 17, and 18, respectively, in which a difference of refractive index from that of the center taken as a standard (0) is depicted as a contour line. In each case, the length of the horizontal line connecting two points on the contour line of the refractive index difference of -0.03 and passing the center was about 1 mm.
It is seen from FIG. 16 that the refractive index of a unit lens of Example 12 changed substantially continuously. The aperture was about 95%, which is much greater than that obtained when circular lenses are arrayed in a closest packing mode (78.5%). The plurality of lens regions formed each had a substantially regular hexagonal shape, the outer edges of which were shared by neighboring regions. The refractive index distribution in each region showed nearly circular and concentric contour lines.
In Comparative Example 6, on the other hand, a large proportion in a unit lens showed no distribution of a refractive index, and the aperture was about 70%. In Comparative Example 7, although an aperture of about 90% was obtained, each unit lens had refractive index distribution shown by hexagonal contour lines and was poor in transmission efficiency.
EXAMPLE 13
Ten parts of poly(methyl acrylate) obtained by solution polymerization, 10 parts of tribromophenoxyethyl acrylate (refractive index: 1.56), 0.1 part of IRGACURE 651, and 20 parts of ethyl acetate were mixed, and the mixture was cast to obtain a 50 μm thick film. The cast film was scanned with a helium-cadmium laser beam having a diameter of 50 μm at a speed of 10 mm/sec. The film was immersed in methanol to remove unreacted tribromophenoxyethyl acrylate to obtain a refractive index-distributed waveguide shown in FIG. 19.
EXAMPLE 14
A waveguide array shown in FIG. 20 was obtained in the same manner as in Example 13, except that the laser beam was scanned along two parallel tracks at a distance of 10 mm to form two parallel refractive index-distributed waveguides.
EXAMPLE 15
A 50 μm thick bifunctional urethane acrylate-based cured sheet was impregnated with a solution of 10 part of tribromophenoxyethyl acrylate and 0.1 part of IRGACURE 651 in 10 parts of chloroform. After removing chloroform in a dark place, the impregnated sheet was irradiated with laser light in the same manner as in Example 13 to obtain a refractive index-distributed waveguide.
EXAMPLE 16
Laser light was linearly scanned on the same impregnated sheet as used in Example 15 in the same manner as in Example 15, then turned in a U-form at a curvature radius of 50 mm, and further linearly scanned to obtain a refractive index-distributed waveguide having a U-form.
COMPARATIVE EXAMPLE 8
The same impregnated sheet as prepared in Example 15 was irradiated with ultraviolet light through an optical mask having 10 μm wide openings at intervals decreasing from 100 μm to 15 μm. Unrelated tribromophenoxyethyl acrylate was removed by extraction to obtain a waveguide array.
Each of the waveguides obtained in Examples 13 to 16 and Comparative Example 8 was evaluated in terms of refractive index distribution in the width direction by means of a differential interference microscope. The results of Example 13 and Comparative Example 8 are shown in FIGS. 21 and 22, respectively. In these FIGS., the refractive index changes in a half side of the waveguide are shown, taking the refractive index at the center as a standard (0).
FIG. 21 reveals a continuous change of refractive index within a waveguiding width of 49 μm. In Comparative Example 8, the waveguide had a width of 1250 μm in which the refractive index changed stepwise. The transmission zone of the waveguide was 260 MHz in Example 13 and 40 MHz in Comparative Example 8. Further, helium-neon laser light was passed through the waveguide to determine the transmission loss. As a result, the transmission loss was 1.7 dB/cm in Example 13 and 3.6 dB/cm in Comparative Example 8.
On the other hand, the transmission zone of each waveguide of the waveguide array obtained in Example 14 was 260 MHz, the same as in Example 13, and that of Examples 15 and 16 was 270 MHz and 210 MHz, respectively. The transmission loss in Example 15 was 1.7 dB/cm, the same as in Example 13.
In addition to the foregoing Examples, a waveguide having a width of 20 μm could be formed by condensing the beam diameter of laser light.
According to the present invention, a polymerization rate-distributed polymer or a crosslinking rate-distributed article can be formed effectively by irradiation using laser light. The process of the present invention is suitable for mass production. An arbitrary distribution pattern can be designed and formed under good control, and distribution regions having a fine shape can be formed with excellent precision. A plurality of distribution regions having a regular shape can be formed at a high density with high precision.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (5)

What is claimed is:
1. A process for producing a lens or a lens array comprising irradiating laser light having a zero-order Gaussian distribution of intensity through an optical mask having a plurality of polygonal openings on a plurality of sites of a matrix base, said matrix base comprising a transparent polymer matrix and a polymerizable photo-reactive substance comprised of a polymerizable monomer and a photo-reactive initiator, to polymerize the monomer and form in the matrix base at least one region in which polymerized monomer is present in a polymerization rate distribution substantially corresponding to a quadratic distribution curve.
2. A process as claimed in claim 1, wherein said photo-reactive substance has a refractive index regulating activity and said lens or lens array has distribution of a refractive index.
3. A process as claimed in claim 1, wherein the process further includes removing unreacted polymerizable monomer after the irradiation to form at least one convex lens region.
4. A process as claimed in claim 1, wherein said matrix base contains not more than 200 parts by weight of said photoreactive substance per 100 parts by weight of the matrix base.
5. A process as claimed in claim 1, wherein said transparent polymer matrix is selected from the group consisting of polyolefins, synthetic rubbers, polyvinyl chloride, polyester, polyamide, cellulose derivatives, polyvinyl alcohol, polyacrylates, polymethacrylates, polyurethane, polyurethane acrylate, and epoxy acrylate resin.
US08/886,422 1992-06-17 1997-07-01 Process for producing polymerization or crosslinking rate-distributed article and process for producing lens, lens array or waveguide using the process Expired - Lifetime US5998096A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/886,422 US5998096A (en) 1992-06-17 1997-07-01 Process for producing polymerization or crosslinking rate-distributed article and process for producing lens, lens array or waveguide using the process

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP18302192A JPH063506A (en) 1992-06-17 1992-06-17 Production of lens and production of lens array plate
JP4-183021 1992-06-17
JP4-250589 1992-08-25
JP25058992A JP3181998B2 (en) 1992-08-25 1992-08-25 Method for producing polymer and method for producing crosslinked product
US7703693A 1993-06-16 1993-06-16
US51191395A 1995-08-07 1995-08-07
US08/886,422 US5998096A (en) 1992-06-17 1997-07-01 Process for producing polymerization or crosslinking rate-distributed article and process for producing lens, lens array or waveguide using the process

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US51191395A Continuation 1992-06-17 1995-08-07

Publications (1)

Publication Number Publication Date
US5998096A true US5998096A (en) 1999-12-07

Family

ID=26501590

Family Applications (1)

Application Number Title Priority Date Filing Date
US08/886,422 Expired - Lifetime US5998096A (en) 1992-06-17 1997-07-01 Process for producing polymerization or crosslinking rate-distributed article and process for producing lens, lens array or waveguide using the process

Country Status (2)

Country Link
US (1) US5998096A (en)
DE (1) DE69316792T2 (en)

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6236493B1 (en) * 1996-04-04 2001-05-22 Institut für Neue Materialien Gemeinnützige GmbH Optical components with a graded-index structure, and method of manufacturing such components
US6242504B1 (en) * 1997-09-29 2001-06-05 Basf Aktiengesellschaft Crosslinking of radiation-crosslinkable pressure-sensitive adhesive films
US6410213B1 (en) * 1998-06-09 2002-06-25 Corning Incorporated Method for making optical microstructures having profile heights exceeding fifteen microns
US20020100990A1 (en) * 2000-09-26 2002-08-01 Platt Ben C. Delivery system for post-operative power adjustment of adjustable lens
EP1234655A1 (en) * 2001-02-26 2002-08-28 Nitto Denko Corporation Plastic object
US6450642B1 (en) 1999-01-12 2002-09-17 California Institute Of Technology Lenses capable of post-fabrication power modification
US6473220B1 (en) 1998-01-22 2002-10-29 Trivium Technologies, Inc. Film having transmissive and reflective properties
US20030003295A1 (en) * 2000-11-27 2003-01-02 Dreher Andreas W. Apparatus and method of correcting higher-order aberrations of the human eye
US20030139486A1 (en) * 2001-12-21 2003-07-24 Jsr Corporation Radiation sensitive refractive index changing composition and refractive index changing method
US20030143391A1 (en) * 2001-06-04 2003-07-31 Lai Shui T. Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US20030185985A1 (en) * 2002-02-01 2003-10-02 Bronikowski Michael J. Method of producing regular arrays of nano-scale objects using nano-structured block-copolymeric materials
US20040008319A1 (en) * 2002-07-11 2004-01-15 Lai Shui T. Optical elements and methods for making thereof
US6682195B2 (en) 2001-10-25 2004-01-27 Ophthonix, Inc. Custom eyeglass manufacturing method
US6712466B2 (en) 2001-10-25 2004-03-30 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US6749632B2 (en) 2000-03-20 2004-06-15 California Institute Of Technology Application of wavefront sensor to lenses capable of post-fabrication power modification
EP1469772A1 (en) * 2001-12-28 2004-10-27 Calhoun Vision, Inc. Customized lenses
US6813082B2 (en) 2000-11-27 2004-11-02 Ophthonix, Inc. Wavefront aberrator and method of manufacturing
US20040235974A1 (en) * 2003-05-21 2004-11-25 Lai Shui T. Apparatus and method for curing of UV-protected UV-curable monomer and polymer mixtures
US20050046957A1 (en) * 2002-07-11 2005-03-03 Lai Shui T. Optical elements and methods for making thereof
US20050190318A1 (en) * 2001-06-14 2005-09-01 Hiroshi Okumura Liquid-crystal display device and method of fabricating the same
US20050260388A1 (en) * 2004-05-21 2005-11-24 Lai Shui T Apparatus and method of fabricating an ophthalmic lens for wavefront correction using spatially localized curing of photo-polymerization materials
US20060088848A1 (en) * 2004-05-05 2006-04-27 Flavio Noca Method for patterning large scale nano-fibrous surfaces using capillography
US20060142528A1 (en) * 2001-12-28 2006-06-29 Calhoun Vision, Inc Initiator and ultraviolet absorber blends for changing lens power by ultraviolet light
US20070099311A1 (en) * 2004-11-01 2007-05-03 Jijie Zhou Nanoscale wicking methods and devices
US20070269488A1 (en) * 2002-11-13 2007-11-22 Nathan Ravi Hydrogel Nanocompsites for Ophthalmic Applications
US20080193749A1 (en) * 2007-02-13 2008-08-14 Thompson D Scott Molded optical articles and methods of making same
US20080203415A1 (en) * 2007-02-13 2008-08-28 3M Innovative Properties Company Led devices having lenses and methods of making same
US7434931B2 (en) 2001-10-25 2008-10-14 Ophthonix Custom eyeglass manufacturing method
US20090174098A1 (en) * 2007-12-06 2009-07-09 Essilor International (Compagnie Generale D'optique) Method for Manufacturing an Ophthalmic Lens Using a Photoactive Material
US7573642B2 (en) 2002-03-26 2009-08-11 Brilliant Film Llc System for collimating backlight
US7573550B2 (en) 2003-05-20 2009-08-11 Brilliant Film, Llc Devices for use in non-emissive displays
US20090233241A1 (en) * 2005-10-03 2009-09-17 Cheng Chao-Min Method of Optical Fabrication of Three-Dimensional Polymeric Structures With Out of Plane Profile Control
US7595934B2 (en) 2002-03-26 2009-09-29 Brilliant Film Llc Integrated sub-assembly having a light collimating or transflecting device
WO2009137220A3 (en) * 2008-05-07 2010-01-14 3M Innovative Properties Company Optical bonding with silicon-containing photopolymerizable composition
US7735998B2 (en) 2006-10-25 2010-06-15 Volk Donald A Multi-layered multifocal lens with blended refractive index
US7740354B2 (en) 2006-10-25 2010-06-22 Volk Donald A Multi-layered gradient index progressive lens
US7744214B2 (en) 1999-07-02 2010-06-29 E-Vision Llc System, apparatus and method for correcting vision with an adaptive optic
US8226253B2 (en) 2008-02-27 2012-07-24 Lubart Neil D Concentrators for solar power generating systems
US9069256B2 (en) 2005-10-03 2015-06-30 Carnegie Mellon University Method of optical fabrication of three-dimensional polymeric structures with out of plane profile control
KR101749367B1 (en) 2009-12-17 2017-06-20 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Display panel assembly and methods of making same
US11266495B2 (en) 2019-10-20 2022-03-08 Rxsight, Inc. Light adjustable intraocular lens with a modulable absorption front protection layer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19928378A1 (en) * 1999-06-21 2000-12-28 Joachim Becker Back-polymerization of photopolymers with application in e.g. dental fillings, occurs at interface opposite entry point, where coating converts incident radiation to new wavelengths initiating setting

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477932A (en) * 1967-11-13 1969-11-11 Monsanto Res Corp Laser radiation-induced polymerization
GB1348911A (en) * 1971-02-05 1974-03-27 Schwarza Chemiefaser Process for the production of synthetic filaments and planar bodies
US3809686A (en) * 1970-03-19 1974-05-07 Bell Telephone Labor Inc Transparent media capable of photoinduced refractive index changes and their application to light guides and the like
US4248959A (en) * 1978-12-07 1981-02-03 American Hoechst Corporation Preparation of diazo printing plates using laser exposure
US4287277A (en) * 1976-07-27 1981-09-01 Canon Kabushiki Kaisha Hologram recording material
US4712854A (en) * 1983-07-11 1987-12-15 Omron Tateisi Electronics Co. Optical waveguide and method of making the same
US4942112A (en) * 1988-01-15 1990-07-17 E. I. Du Pont De Nemours And Company Photopolymerizable compositions and elements for refractive index imaging
US5164223A (en) * 1990-10-05 1992-11-17 Nippon Sheet Glass Co., Ltd. Process for producing light control plate
US5191358A (en) * 1990-03-16 1993-03-02 Brother Kogyo Kabushiki Kaisha Light scanning device with microlenses having a same power density distribution as a power density distribution of a photosetting light beam
US5541247A (en) * 1991-10-22 1996-07-30 Koike; Yasuhiro Optical resin materials with distributed refractive index, process for producing the materials, and optical conductors using the materials

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3477932A (en) * 1967-11-13 1969-11-11 Monsanto Res Corp Laser radiation-induced polymerization
US3809686A (en) * 1970-03-19 1974-05-07 Bell Telephone Labor Inc Transparent media capable of photoinduced refractive index changes and their application to light guides and the like
GB1348911A (en) * 1971-02-05 1974-03-27 Schwarza Chemiefaser Process for the production of synthetic filaments and planar bodies
US4287277A (en) * 1976-07-27 1981-09-01 Canon Kabushiki Kaisha Hologram recording material
US4248959A (en) * 1978-12-07 1981-02-03 American Hoechst Corporation Preparation of diazo printing plates using laser exposure
US4712854A (en) * 1983-07-11 1987-12-15 Omron Tateisi Electronics Co. Optical waveguide and method of making the same
US4942112A (en) * 1988-01-15 1990-07-17 E. I. Du Pont De Nemours And Company Photopolymerizable compositions and elements for refractive index imaging
US5191358A (en) * 1990-03-16 1993-03-02 Brother Kogyo Kabushiki Kaisha Light scanning device with microlenses having a same power density distribution as a power density distribution of a photosetting light beam
US5164223A (en) * 1990-10-05 1992-11-17 Nippon Sheet Glass Co., Ltd. Process for producing light control plate
US5541247A (en) * 1991-10-22 1996-07-30 Koike; Yasuhiro Optical resin materials with distributed refractive index, process for producing the materials, and optical conductors using the materials

Cited By (108)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6236493B1 (en) * 1996-04-04 2001-05-22 Institut für Neue Materialien Gemeinnützige GmbH Optical components with a graded-index structure, and method of manufacturing such components
US6242504B1 (en) * 1997-09-29 2001-06-05 Basf Aktiengesellschaft Crosslinking of radiation-crosslinkable pressure-sensitive adhesive films
US20060023289A1 (en) * 1998-01-22 2006-02-02 Clikeman Richard W Device having reflective and transmissive properties
US7236286B2 (en) 1998-01-22 2007-06-26 Brilliant Film Llc Device having reflective and transmissive properties
US6473220B1 (en) 1998-01-22 2002-10-29 Trivium Technologies, Inc. Film having transmissive and reflective properties
US6410213B1 (en) * 1998-06-09 2002-06-25 Corning Incorporated Method for making optical microstructures having profile heights exceeding fifteen microns
US6620576B2 (en) * 1998-06-09 2003-09-16 Corning Incorporated Methods of making structures from photosensitive coatings having profile heights exceeding fifteen microns
US20030093150A1 (en) * 1999-01-12 2003-05-15 Jethmalani Jagdish M. Lanses capable of post-fabrication power modification
US6450642B1 (en) 1999-01-12 2002-09-17 California Institute Of Technology Lenses capable of post-fabrication power modification
US20030090624A1 (en) * 1999-01-12 2003-05-15 Jethmalani Jagdish M. Lenses capable of post-fabrication power modification
US6813097B2 (en) 1999-01-12 2004-11-02 California Institute Of Technology Lenses capable of post-fabrication modulus change
US7837326B2 (en) 1999-01-12 2010-11-23 Calhoun Vision, Inc. Lenses capable of post-fabrication power modification
US7210783B2 (en) 1999-01-12 2007-05-01 California Institute Of Technology Lenses capable of post-fabrication power modification
US20030151719A1 (en) * 1999-01-12 2003-08-14 Jethmalani Jagdish M. Lenses capable of post-fabrication modulus change
US20030090013A1 (en) * 1999-01-12 2003-05-15 Jethmalani Jagdish M. Lenses capable of post-fabrication power modification
US6824266B2 (en) 1999-01-12 2004-11-30 California Institute Of Technology Lenses capable of post-fabrication power modification
US7744214B2 (en) 1999-07-02 2010-06-29 E-Vision Llc System, apparatus and method for correcting vision with an adaptive optic
US6749632B2 (en) 2000-03-20 2004-06-15 California Institute Of Technology Application of wavefront sensor to lenses capable of post-fabrication power modification
US7105110B2 (en) 2000-09-26 2006-09-12 Calhoun Vision, Inc. Delivery system for post-operative power adjustment of adjustable lens
US6905641B2 (en) 2000-09-26 2005-06-14 Calhoun Vision, Inc. Delivery system for post-operative power adjustment of adjustable lens
US20020100990A1 (en) * 2000-09-26 2002-08-01 Platt Ben C. Delivery system for post-operative power adjustment of adjustable lens
US20060261502A1 (en) * 2000-09-26 2006-11-23 Platt Ben C Delivery system for post-operative power adjustment of adjustable lens
US20050192563A1 (en) * 2000-09-26 2005-09-01 Calhoun Vision, Inc. Delivery system for post-operative power adjustment of adjustable lens
US7695134B2 (en) 2000-11-27 2010-04-13 Ophthonix, Inc. Apparatus and method of correcting higher-order aberrations of the human eye
US6813082B2 (en) 2000-11-27 2004-11-02 Ophthonix, Inc. Wavefront aberrator and method of manufacturing
US7293871B2 (en) 2000-11-27 2007-11-13 Ophthonix, Inc. Apparatus and method of correcting higher-order aberrations of the human eye
US20080252845A1 (en) * 2000-11-27 2008-10-16 Dreher Andreas W Apparatus and method of correcting higher-order aberrations of the human eye
US20050052747A1 (en) * 2000-11-27 2005-03-10 Bruns Donald G. Wavefront aberrator and method of manufacturing
US6989938B2 (en) 2000-11-27 2006-01-24 Ophthonix, Inc. Wavefront aberrator and method of manufacturing
US20030003295A1 (en) * 2000-11-27 2003-01-02 Dreher Andreas W. Apparatus and method of correcting higher-order aberrations of the human eye
EP1234655A1 (en) * 2001-02-26 2002-08-28 Nitto Denko Corporation Plastic object
US7217375B2 (en) * 2001-06-04 2007-05-15 Ophthonix, Inc. Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US20030143391A1 (en) * 2001-06-04 2003-07-31 Lai Shui T. Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US7123337B2 (en) * 2001-06-14 2006-10-17 Nec Lcd Technologies, Ltd. Liquid-crystal display device and method of fabricating the same
US20050190318A1 (en) * 2001-06-14 2005-09-01 Hiroshi Okumura Liquid-crystal display device and method of fabricating the same
US6840619B2 (en) 2001-10-25 2005-01-11 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US7021764B2 (en) 2001-10-25 2006-04-04 Ophtohonix, Inc. Eyeglass manufacturing method using variable index layer
US7988284B2 (en) 2001-10-25 2011-08-02 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US6942339B2 (en) 2001-10-25 2005-09-13 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US7931368B2 (en) 2001-10-25 2011-04-26 Opthonix, Inc. Eyeglass manufacturing method using variable index layer
US7857446B2 (en) 2001-10-25 2010-12-28 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US7845797B2 (en) 2001-10-25 2010-12-07 Ophthonix, Inc. Custom eyeglass manufacturing method
US20040160574A1 (en) * 2001-10-25 2004-08-19 Dreher Andreas W. Eyeglass manufacturing method using variable index layer
US7588333B2 (en) 2001-10-25 2009-09-15 Ophthonix, Inc. Improving vision in macular degeneration patients
US20070171359A1 (en) * 2001-10-25 2007-07-26 Dreher Andreas W Eyeglass manufacturing method using variable index layer
US7503651B2 (en) 2001-10-25 2009-03-17 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US20090051871A1 (en) * 2001-10-25 2009-02-26 Laurence Warden Custom eyeglass manufacturing method
US20050036106A1 (en) * 2001-10-25 2005-02-17 Dreher Andreas W. Eyeglass manufacturing method using variable index layer
US6682195B2 (en) 2001-10-25 2004-01-27 Ophthonix, Inc. Custom eyeglass manufacturing method
US7434931B2 (en) 2001-10-25 2008-10-14 Ophthonix Custom eyeglass manufacturing method
US6712466B2 (en) 2001-10-25 2004-03-30 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
US7249847B2 (en) 2001-10-25 2007-07-31 Ophthonix, Inc. Eyeglass manufacturing method using variable index layer
AU2002323913B2 (en) * 2001-12-21 2007-10-18 Jsr Corporation Radiation sensitive refractive index changing composition and refractive index changing method
US6787289B2 (en) * 2001-12-21 2004-09-07 Jsr Corporation Radiation sensitive refractive index changing composition and refractive index changing method
US20030139486A1 (en) * 2001-12-21 2003-07-24 Jsr Corporation Radiation sensitive refractive index changing composition and refractive index changing method
EP1469772A1 (en) * 2001-12-28 2004-10-27 Calhoun Vision, Inc. Customized lenses
US20060142528A1 (en) * 2001-12-28 2006-06-29 Calhoun Vision, Inc Initiator and ultraviolet absorber blends for changing lens power by ultraviolet light
EP1469772A4 (en) * 2001-12-28 2008-10-29 Calhoun Vision Inc Customized lenses
US7115305B2 (en) 2002-02-01 2006-10-03 California Institute Of Technology Method of producing regular arrays of nano-scale objects using nano-structured block-copolymeric materials
US7700157B2 (en) 2002-02-01 2010-04-20 California Institute Of Technology Method of producing regular arrays of nano-scale objects using nano-structured block-copolymeric materials
US20060286297A1 (en) * 2002-02-01 2006-12-21 Bronikowski Michael J Method of producing regular arrays of nano-scale objects using nano-structured block-copolymeric materials
US20030185985A1 (en) * 2002-02-01 2003-10-02 Bronikowski Michael J. Method of producing regular arrays of nano-scale objects using nano-structured block-copolymeric materials
US7595934B2 (en) 2002-03-26 2009-09-29 Brilliant Film Llc Integrated sub-assembly having a light collimating or transflecting device
US7573642B2 (en) 2002-03-26 2009-08-11 Brilliant Film Llc System for collimating backlight
US20080254210A1 (en) * 2002-07-11 2008-10-16 Lai Shui T Optical elements and methods for making thereof
US6934088B2 (en) 2002-07-11 2005-08-23 Ophthonix, Inc. Optical elements and methods for making thereof
US20050064105A1 (en) * 2002-07-11 2005-03-24 Lai Shui T. Optical elements and methods for making thereof
US7420743B2 (en) 2002-07-11 2008-09-02 Ophthonix, Inc. Optical elements and methods for making thereof
US20050046957A1 (en) * 2002-07-11 2005-03-03 Lai Shui T. Optical elements and methods for making thereof
US20050057815A1 (en) * 2002-07-11 2005-03-17 Lai Shui T. Optical elements and methods for making thereof
US6976641B2 (en) 2002-07-11 2005-12-20 Ophthonix, Inc. Optical elements and methods for making thereof
US20040008319A1 (en) * 2002-07-11 2004-01-15 Lai Shui T. Optical elements and methods for making thereof
US6836371B2 (en) 2002-07-11 2004-12-28 Ophthonix, Inc. Optical elements and methods for making thereof
US8790104B2 (en) 2002-10-03 2014-07-29 Essilor International (Compagnie Generale D'optique Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US20090212465A1 (en) * 2002-10-03 2009-08-27 Lai Shui T Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US20080088938A1 (en) * 2002-10-03 2008-04-17 Lai Shui T Apparatus and method of fabricating a compensating element for wavefront correction using spatially localized curing of resin mixtures
US20070269488A1 (en) * 2002-11-13 2007-11-22 Nathan Ravi Hydrogel Nanocompsites for Ophthalmic Applications
US8153156B2 (en) 2002-11-13 2012-04-10 The United States Of America As Represented By The Department Of Veteran Affairs Hydrogel nanocompsites for ophthalmic applications
US7573550B2 (en) 2003-05-20 2009-08-11 Brilliant Film, Llc Devices for use in non-emissive displays
US20080297888A1 (en) * 2003-05-21 2008-12-04 Lai Shui T Apparatus and method for curing of uv-protected uv-curable monomer and polymer mixtures
US20040235974A1 (en) * 2003-05-21 2004-11-25 Lai Shui T. Apparatus and method for curing of UV-protected UV-curable monomer and polymer mixtures
US20060088848A1 (en) * 2004-05-05 2006-04-27 Flavio Noca Method for patterning large scale nano-fibrous surfaces using capillography
US7491628B2 (en) 2004-05-05 2009-02-17 California Institute Of Technology Method for patterning large scale nano-fibrous surfaces using capillography
US20080123197A1 (en) * 2004-05-21 2008-05-29 Lai Shui T Apparatus and method of fabricating an ophthalmic lens for wavefront correction using spatially localized curing of photo-polymerization materials
US20050260388A1 (en) * 2004-05-21 2005-11-24 Lai Shui T Apparatus and method of fabricating an ophthalmic lens for wavefront correction using spatially localized curing of photo-polymerization materials
WO2006029268A2 (en) * 2004-09-07 2006-03-16 Ophthonix, Inc. Optical elements and methods for making thereof
WO2006029268A3 (en) * 2004-09-07 2006-10-05 Ophthonix Inc Optical elements and methods for making thereof
US8021967B2 (en) 2004-11-01 2011-09-20 California Institute Of Technology Nanoscale wicking methods and devices
US20070099311A1 (en) * 2004-11-01 2007-05-03 Jijie Zhou Nanoscale wicking methods and devices
US9069256B2 (en) 2005-10-03 2015-06-30 Carnegie Mellon University Method of optical fabrication of three-dimensional polymeric structures with out of plane profile control
US8192922B2 (en) * 2005-10-03 2012-06-05 Carnegie Mellon University Method of optical fabrication of three-dimensional polymeric structures with out of plane profile control
US20090233241A1 (en) * 2005-10-03 2009-09-17 Cheng Chao-Min Method of Optical Fabrication of Three-Dimensional Polymeric Structures With Out of Plane Profile Control
US7735998B2 (en) 2006-10-25 2010-06-15 Volk Donald A Multi-layered multifocal lens with blended refractive index
US7740354B2 (en) 2006-10-25 2010-06-22 Volk Donald A Multi-layered gradient index progressive lens
CN101627477B (en) * 2007-02-13 2011-05-11 3M创新有限公司 Molded optical articles and methods of making same
US20080203415A1 (en) * 2007-02-13 2008-08-28 3M Innovative Properties Company Led devices having lenses and methods of making same
WO2008100719A1 (en) * 2007-02-13 2008-08-21 3M Innovative Properties Company Molded optical articles and methods of making same
US9944031B2 (en) 2007-02-13 2018-04-17 3M Innovative Properties Company Molded optical articles and methods of making same
US8330176B2 (en) 2007-02-13 2012-12-11 3M Innovative Properties Company LED devices having lenses and methods of making same
US20080193749A1 (en) * 2007-02-13 2008-08-14 Thompson D Scott Molded optical articles and methods of making same
US8901588B2 (en) 2007-02-13 2014-12-02 3M Innovative Properties Company LED devices having lenses and methods of making same
US20090174098A1 (en) * 2007-12-06 2009-07-09 Essilor International (Compagnie Generale D'optique) Method for Manufacturing an Ophthalmic Lens Using a Photoactive Material
US8226253B2 (en) 2008-02-27 2012-07-24 Lubart Neil D Concentrators for solar power generating systems
US20110171400A1 (en) * 2008-05-07 2011-07-14 David Scott Thompson Optical bonding with silicon-containing photopolymerizable composition
WO2009137220A3 (en) * 2008-05-07 2010-01-14 3M Innovative Properties Company Optical bonding with silicon-containing photopolymerizable composition
KR101749367B1 (en) 2009-12-17 2017-06-20 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Display panel assembly and methods of making same
US10738172B2 (en) 2009-12-17 2020-08-11 3M Innovative Properties Company Display panel assembly and methods of making same
US11266495B2 (en) 2019-10-20 2022-03-08 Rxsight, Inc. Light adjustable intraocular lens with a modulable absorption front protection layer

Also Published As

Publication number Publication date
DE69316792D1 (en) 1998-03-12
DE69316792T2 (en) 1998-05-28

Similar Documents

Publication Publication Date Title
US5998096A (en) Process for producing polymerization or crosslinking rate-distributed article and process for producing lens, lens array or waveguide using the process
KR100603657B1 (en) Optical structures for diffusing light
US4712854A (en) Optical waveguide and method of making the same
US6671095B2 (en) Micro relief element and preparation thereof
EP0575885B1 (en) Process for producing polymerization or crosslinking rate-distributed article and process for producing lens, lens array or waveguide using the process
EP0392868A2 (en) Method of producing light control plate which induces scattering of light at different angles
WO1991018304A3 (en) Improvements in or relating to microlens screens, photopolymerisable materials and artifacts utilising the same
JPH0618739A (en) Production of waveguide
JP3575860B2 (en) Diffuser manufacturing method and diffuser
KR101441721B1 (en) Method for manufacturing surface unevenness
KR100448606B1 (en) Manufacturing method of light diffusing screen
JP2837239B2 (en) Manufacturing method of light control plate with light scattering transparent region
JPH0675105A (en) Lens array plate and its production
JP3504683B2 (en) Method of forming lens region, lens and lens array plate
JPH063506A (en) Production of lens and production of lens array plate
US5137801A (en) Process for producing light control plate having light-scattering pervious region
JP3181998B2 (en) Method for producing polymer and method for producing crosslinked product
EP0409396B1 (en) Process for producing light control plate having light-scattering pervious region
JPH06331822A (en) Filter type lens, lens array plate, its production, and device utilizing same
JPH0627303A (en) Lens plate and its production
JPS6153031A (en) Manufacture of refractive index distributed type micro lens
JP3490732B2 (en) Manufacturing method of plastic aspherical microlens
JPH06130206A (en) Lens, microlens array plate and its production
JPH02310501A (en) Production of flat plate microlens array made of synthetic resin
Ferm et al. Optical Array Fabrication via Photoimaging of Acrylate Monomers

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12